Detergent compositions containing and effervescent

ABSTRACT

Low density detergent compositions, containing sulfate and an acidic dispersing aid combined with an alkaline source, which are capable of reacting together to produce a gas, are suitable for use in laundry washing methods.

TECHNICAL FIELD

The present invention relates to preferably a low density detergentcomposition containing sulphate, an acid dispersing aid and an alkalisource, which is suitable for use in laundry washing methods.

BACKGROUND OF THE INVENTION

Detergent compositions, especially low density detergent compositionsoften contain high levels of sulphates. A problem encountered with thesedetergents can be the poor solubility properties of one or morecomponents in the detergent. A consequence of this in a typical washingprocess can be poor dispensing of the product, either from thedispensing drawer of a washing machine, or from a dosing device placedwith the laundry inside the machine. This can reduces the effectivenessof the powder. This is a particular problem at low water pressuresand/or at lower washing temperatures.

The prior art teaches various ways to improve the solubility of highbulk density detergent compositions. WO95/14767 relates to the poordispensing of high density, non-spray-dried detergent powders, anddiscloses the use of a citric acid salt which has a Rosin Rammlerparticle size of less than 800 microns. WO94/28098 discloses anon-spray-dried detergent powder comprising a combination of anethoxylated primary C8-18 alcohol, an alkali metal aluminosilicatebuilder and 5 to 40wt % of a water-soluble salt of a citric acid.

The use of effervescence to improve the dispersability of granularmaterials has been used extensively in pharmaceutical preparations. Themost widely used effervescent system in this respect is citric acid incombination with bicarbonate. This effervescent system has also beendescribed for improving the dispersabality of pesticidal compositionsfor controlling water-bore pests, e.g. GB-A-2,184,946.

It has now been found that particularly in low density detergentcompositions, comprising high levels of sulphate, poor dispersing canlead to insolubility/precipitation of certain components (present in thewashing water) onto the fabrics in the wash and onto the washingmachine. In particular, it has been found that calcium and magnesiumcarbonate and limesoaps, formed by the water hardness, can precipitateonto the fabric. It has been found that this can even occur whenbuilders (which are traditionally employed in detergents to counter theadverse effect on detergency of water hardness ions) are present.

Without wishing to be bound by theory, the Applicants believe that thisis due to increased ionic strength, due to the high level of sulphatespresent in the washing water. The Applicants have now found that thisproblem can be solved by the use of a specific dispersing aid. It hasbeen found that the precipitation of various components, such asmagnesium and calcium carbonates and lime soaps, can be reduced in a lowdensity detergent composition containing sulphate, an alkali source andincorporating a dispersing aid which is an acid source, can react withthe alkali source to produce a gas, and which can also act as awater-soluble dispersant or builder material.

It is believed that the reaction of the acid source and the alkalisource which produces gas (preferably carbon dioxide) firstly helps thedispersion and dispensing of the detergent, reducing deposition of(detergent) components on fabrics and the machine. In addition, buildermaterials will be dispensed more effectively so that calcium andmagnesium ions are rapidly contacted with builder material, therebyquickly and effectively reducing the free calcium and magnesium in thewater so that the formation of undesirably precipitates is substantiallyreduced. Furthermore, once in the wash water acid is de-protonated andthe base form of the acid can act as a dispersant or builder, furtherreducing the free calcium and magnesium in the water and furtherreducing the formation of undesirable precipitates.

All documents cited in the present description are incorporated hereinby reference.

SUMMARY OF THE INVENTION

The present invention relates to detergent compositions comprisingsulphate, an acid dispersing aid and an alkali source wherein said aciddispersing aid and said alkali source are capable of reacting togetherin the presence of water to produce a gas. The ratio of sulphate to aciddispersing aid is 13.5:1 or less, or the level of acid dispersing aid isat least 1.5% by weight of the detergent composition. Preferably thedetergent composition is a low density detergent composition.

DETAILED DESCRIPTION OF THE INVENTION

According to a first aspect of the invention there is provided adetergent composition comprising at least 15% by weight of a sulphatesalt, an acid dispersing aid and an alkali source wherein said aciddispersing aid and alkali source are capable of reacting together in thepresence of water to produce a gas, and wherein the weight ratio ofsulphate salt to said acid dispersing aid is from 13.5:1 or less.

According to a second aspect of the invention there is provided adetergent composition comprising at least 15% by weight of a sulphatesalt, an acid dispersing aid and an alkali source wherein said aciddispersing aid and alkali source are capable of reacting together in thepresence of water to produce a gas, and wherein the level of aciddispersing aid is at least 1.5% by weight of the detergent composition.

Preferably the gas produced is carbon dioxide, and therefore the alkalisource is preferably bicarbonate or carbonate.

In accordance with the invention the acid dispersing aid, which iscapable of reacting with the alkali source to produce a gas, ispreferably capable of building and/or dispersing free ions such ascalcium and magnesium ions, present in the wash.

The granular detergent compositions in accordance with the presentinvention generally have a bulk density of at least 500 g/liter,preferably less than 850 g/liter more preferably from 600 g/liter to 750g/liter.

Sulphate Salt

In the present invention the ratio of sulphate salt to the acidicdispersing aid is preferably from 12:1 to 1:1, most preferably from 11:1to 2:1.

The sulphate salt can be present in the detergent composition in anyform, preferably it is an inorganic sulphate salt, such as sodiumsulphate, magnesium sulphate, ammonium sulphate or mixtures of variousforms of sulphate. The sulphate preferably is substantially anhydrous,(i.e. generally no greater than 50% by weight of the sulphate saltcontaining water, preferably no greater than 25%, more preferably nogreater than 15%, most preferably no greater than 10%), preferably it isanhydrous sodium sulphate. This is preferably combined with a smallamount of magnesium sulphate, preferably of from 0.2% to 5% by weight ofthe composition.

Acid Dispersing Aid

The acid dispersing aid is a component capable of reacting with thesource of alkali in the presence of water to produce a gas.

In the first aspect of the present invention the ratio of sulphate saltto the acid dispersing aid is 13.5:1 or less, more preferably from 12:1to 1:1, most preferably from 11:1 to 2:1. The acid dispersing aid ispreferably present at a level of from 0.05% to 25%, more preferably at alevel of 0.5% to 15%, even more preferably of from 1% to 10%, even morepreferably from 1% to 7%, most preferably of from 2% to 5% by weight ofthe detergent composition.

In the second aspect of the invention the level of the acid dispersingaid is at least 1.5% or more, preferably from 2% to 7% by weight of thecomposition.

Preferably, the detergent composition comprises at least 1.5% by weightof acid dispersing aid and 20.25% by weight of sulphate salts, in aratio of sulphate salt to acid dispersing aid is from 13.5:1 or less.

In accordance with the invention the acid dispersing aid, which iscapable of reacting with the alkali source to produce a gas, ispreferably capable of building and/or dispersing free ions such ascalcium and magnesium ions, present in the wash.

Preferably, 80% or more of the acid dispersing aid has a particle sizein the range of from about 150 microns to about 710 microns, with atleast about 37% by weight of the acid source having a particle size ofabout 350 microns or less. More preferably 100% of the acid compound hasa particle size of about 710 microns or less. Further preferred aciddispersing aids are such that more than about 38%, more preferably38.7%, of the acidic compound has a particle size of about 350 micronsor less.

The particle size of the acidic compound is calculated by sieving asample of the source of acidity on a series of Tyler sieves. Forexample, a Tyler sieve mesh 100 corresponds to an aperture size of 150microns. The weight fractions thereby obtained are plotted against theaperture size of the sieves.

The acid dispersing aid may be any suitable organic, mineral orinorganic acid, or a derivative thereof, or a mixture thereof. Theacidic compound may be a mono-, bi- or tri-protonic acid. Preferably,the compound is a tri-protonic acid. Preferred derivatives include asalt or ester of the acid. The acid compound is preferablynon-hygroscopic, which can improve storage stability. Organic acids andoptionally their derivatives are preferred. The acid is preferablywater-soluble. Most preferably the acid dispersing aid is selected suchthat its base form, formed in solution or after reaction with a alkalinesource, can built and/or disperse free ions, such as calcium andmagnesium ions, present in the wash.

Suitable acids include citric, glutaric, tartaric succinic or adipicacid, monosodium phosphate, boric acid, or a salt or an ester thereof.Citric acid is especially preferred.

Alkali Source

In accordance with the present invention, an alkali source is presentsuch that it has the capacity to react with the source of aciddispersing aid to produce a gas. Preferably this gas is carbon dioxide,and therefore the alkali is a carbonate, or suitable derivative thereof.

The detergent composition of the present invention preferably containsfrom about 2% to about 75%, preferably from about 5% to about 60%, mostpreferably from about 10% to about 30% by weight of the alkali source.When the alkali source is present in an agglomerated detergent particle,the agglomerate preferably contains from about 10% to about 60% of thealkali source.

In accordance with the invention the acid dispersing aid, which iscapable of reacting with the alkali source to produce a gas, ispreferably capable of building and/or dispersing free ions such ascalcium and magnesium ions, present in the wash.

In a preferred embodiment, the alkali source is a carbonate. Examples ofpreferred carbonates are the alkaline earth and alkali metal carbonates,including sodium carbonate, bicarbonate and sesqui-carbonate and anymixtures thereof with ultra-fine calcium carbonate such as are disclosedin German Patent Application No. 2,321,001 published on Nov. 15, 1973.Alkali metal percarbonate salts are also suitable sources of carbonatespecies and are described in more detail in the section ‘inorganicperhydrate salts’ herein.

The carbonate and bicarbonate preferably have a amorphous structure.Preferably the carbonate and bicarbonates are coated with coatingmaterials. The particles of carbonate and bicarbonate can have a meanparticle size of 250 μm or greater, preferably 500 μm or greater. It ispreferred that fewer than 20% of the particles have a particle sizebelow 500 μm.

The mean particle size of the particles of carbonate and bicarbonateherein is determined by reference to a method involving choice of variedsizes of sieve through which the sample is attempted to be passed. Themean particle size of a sample is given by the diameter of sieve throughwhich half of the mass of the sample will pass, and accordingly throughwhich half of the sample will not pass.

The alkalinity system may include other components, such as is asilicate. Suitable silicates include the water soluble sodium silicateswith an SiO₂: Na₂O ratio of from 1.0 to 2.8, with ratios of from 1.6 to2.0 being preferred, and 2.0 ratio being most preferred. The silicatesmay be in the form of either the anhydrous salt or a hydrated salt.Sodium silicate with an SiO₂:Na₂O ratio of 2.0 is the most preferredsilicate. Alkali metal persilicates are also suitable sources ofsilicate herein.

Suitable silicates include the sodium silicates with an SiO₂:Na₂O ratioof from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and2.0 ratio being most preferred. The silicates may be in the form ofeither the anhydrous salt or a hydrated salt. Sodium silicate with anSiO₂:Na₂O ratio of 2.0 is the most preferred silicate. Preferably thesilicates have an amorphous structure.

Other suitable sources will be known to those skilled in the art.

Additional Detergent Components

The detergent compositions of the invention may also contain additionaldetergent components. The precise nature of these additional components,and levels of incorporation thereof will depend on the physical form ofthe composition, and the precise nature of the washing operation forwhich it is to be used.

The compositions of the invention preferably contain one or moreadditional detergent components selected from surfactants, bleaches,builders, organic polymeric compounds, enzymes, suds suppressors, limesoap dispersants, soil suspension and anti-redeposition agents andcorrosion inhibitors.

Surfactant

The detergent compositions of the invention preferably contains one ormore surfactants selected from anionic, nonionic, cationic, ampholytic,amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of anionic, nonionic, ampholytic, and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Furtherexamples are given in “Surface Active Agents and Detergents” (Vol. I andII by Schwartz, Perry and Berch). A list of suitable cationicsurfactants is given in U.S. Pat. No. 4,259,217 issued to Murphy on Mar.31, 1981.

Where present, ampholytic, amphoteric and zwitterionic surfactants aregenerally used in combination with one or more anionic and/or nonionicsurfactants.

Anionic Surfactant

A preferred additional component of the detergent composition of theinvention is an anionic surfactant. Any anionic surfactants useful fordetersive purposes are suitable. Examples include salts (including, forexample, sodium, potassium, ammonium, and substituted ammonium saltssuch as mono-, di- and triethanolamine salts) of the anionic sulfate,sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfatesurfactants are preferred.

Other anionic surfactants include the isethionates such as the acylisethionates, N-acyl taurates, fatty acid amides of methyl tauride,alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆-C₁₄ diesters),N-acyl sarcosinates. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.

The weight ratio of anionic surfactant to cationic ester surfactant inthe surfactant system is from 3:1 to 15:1, preferably from 4:1 to 12:1,most preferably from 5:1 to 10:1.

Anionic Sulfate Surfactant

Anionic sulfate surfactants suitable for use herein include the linearand branched primary and secondary alkyl sulfates, alkyl ethoxysulfates,fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ethersulfates, the C₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl)glucamine sulfates, and sulfates of alkylpolysaccharides such as thesulfates of alkylpolyglucoside (the nonionic nonsulfated compounds beingdescribed herein).

Alkyl sulfate surfactants are preferably selected from the linear andbranched primary C₉-C₂₂ alkyl sulfates, more preferably the C₁₁-C₁₅branched chain alkyl sulfates and the C₁₂-C₁₄ linear chain alkylsulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the groupconsisting of the C₁₀-C₁₈ alkyl sulfates which have been ethoxylatedwith from 0.5 to 20 moles of ethylene oxide per molecule. Morepreferably, the alkyl ethoxysulfate surfactant is a C₁₁-C₁₈, mostpreferably C₁₁-C₁₅ alkyl sulfate which has been ethoxyiated with from0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of thepreferred alkyl sulfate and alkyl ethoxysulfate surfactants. Suchmixtures have been disclosed in PCT Patent Application No. WO93/18124.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use herein include the saltsof C₅-C₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C₆-C₂₂primary or secondary alkane sulfonates, C₆-C₂₄ olefin sulfonates,sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixturesthereof.

Anionic Carboxylate Surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxy polycarboxylate surfactants and thesoaps (‘alkyl carboxyls’), especially certain secondary soaps asdescribed herein.

Suitable alkyl ethoxy carboxylates include those with the formulaRO(CH₂CH₂O)_(x)CH₂COO⁻M⁺ wherein R is a C₆ to C₁₈ alkyl group, x rangesfrom 0 to 10, and the ethoxylate distribution is such that, on a weightbasis, the amount of material where x is 0 is less than 20% and M is acation. Suitable alkyl polyethoxy polycarboxylate surfactants includethose having the formula RO—(CHR₁-CHR₂—O)—R₃ wherein R is a C₆ to C₁₈alkyl group, x is from 1 to 25, R₁ and R₂ are selected from the groupconsisting of hydrogen, methyl acid radical, succinic acid radical,hydroxysuccinic acid radical, and mixtures thereof, and R₃ is selectedfrom the group consisting of hydrogen, substituted or unsubstitutedhydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants whichcontain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoicacid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certainsoaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates offormula R—CON(R¹)CH₂COOM, wherein R is a C₅-C₁₇ linear or branched alkylor alkenyl group, R¹ is a C₁-C₄ alkyl group and M is an alkali metalion. Preferred examples are the myristyl and oleoyl methyl sarcosinatesin the form of their sodium salts.

Alkoxylated Nonionic Surfactant

A preferred additional surfactant in accord with the detergentcomposition of the invention is a nonionic surfactant present at a levelof from 0.1% to 20%, more preferably from 0.2% to 10% by weight, mostpreferably from 0.5% to 5% by weight of the detergent composition.

Essentially any alkoxylated nonionic surfactants are suitable herein.The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes ofthe nonionic condensates of alkyl phenols, nonionic ethoxylatedalcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionicethoxylate/propoxylate condensates with propylene glycol, and thenonionic ethoxylate condensation products with propylene oxide/ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactant

The condensation products of aliphatic alcohols with from 1 to 25 molesof alkylene oxide, particularly ethylene oxide and/or propylene oxide,are suitable for use herein. The alkyl chain of the aliphatic alcoholcan either be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms. Particularly preferred are thecondensation products of alcohols having an alkyl group containing from8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per moleof alcohol.

Nonionic polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those havingthe structural formula R²CONR¹Z wherein: R1 is H, C₁-C₄ hydrocarbyl,2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixturethereof, preferable C₁-C₄ alkyl, more preferably C₁ or C₂ alkyl, mostpreferably C₁ alkyl (i.e., methyl); and R₂ is a C₅-C₃₁ hydrocarbyl,preferably straight-chain C₅-C₁₉ alkyl or alkenyl, more preferablystraight-chain C₉-C₁₇ alkyl or alkenyl, most preferably straight-chainC₁₁-C₁₇ alkyl or alkenyl, or mixture thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl.

A preferred nonionic polyhydroxy fatty acid amide surfactant for useherein is a C₁₅-C₁₇ alkyl N-methyl glucamide. The ratio of polyhydroxyfatty acid amide to cationic ester surfactant is preferably between 1:1to 1:8, more preferably 1:2.5. It has been found that such surfactantsystems are able to reduce ‘lime soap’ formation and deposition ofencrustation on the fabric.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those having the formula:R⁶CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7 to 21,preferably from 9 to 17 carbon atoms and each R⁷ is selected from thegroup consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, and—(C₂H₄O)_(x)H, where x is in the range of from 1 to 3.

Nonionic Alkylpolysaccharide Surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from 6 to 30 carbon atoms and a polysaccharide, e.g., apolyglycoside, hydrophilic group containing from 1.3 to 10 saccharideunits.

Preferred alkylpolyglycosides have the formula

R²O(C_(n)H_(2n)O)t(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived fromglucose.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formulaR³(OR⁴)_(x)N⁰(R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containingfrom 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene groupcontaining from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl groupcontaining from 1 to 3, or a polyethylene oxide group containing from 1to 3 ethylene oxide groups. Preferred are C₁₀-C₁₈ alkyl dimethylamineoxide, and C₁₀₋₁₈ acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, N.J.

Zwitterionic Surfactant

Zwitterionic surfactants can also be incorporated into the detergentcompositions hereof. These surfactants can be broadly described asderivatives of secondary and tertiary amines, derivatives ofheterocyclic secondary and tertiary amines, or derivatives of quaternaryammonium, quaternary phosphonium or tertiary sulfonium compounds.Betaine and sultaine surfactants are exemplary zwitterionic surfactantsfor use herein.

Suitable betaines are those compounds having the formula R(R′)₂N⁺R²COO⁻wherein R is a C₆-C₁₈ hydrocarbyl group, each R¹ is typically C₁-C₃alkyl, and R² is a C₁-C₅ hydrocarbyl group. Preferred betaines areC₁₂₋₁₈ dimethyl-ammonia hexanoate and the C₁₀₋₁₈ acylamidopropane (orethane) dimethyl (or diethyl) betaines. Complex betaine surfactants arealso suitable for use herein.

Cationic Surfactants

Cationic surfactants can also be used in the detergent compositionsherein. Suitable cationic surfactants include the quaternary ammoniumsurfactants selected from mono C₆-C₁₆, preferably C₆-C₁₀ N-alkyl oralkenyl ammonium surfactants wherein the remaining N positions aresubstituted by methyl, hydroxyethyl or hydroxypropyl groups.

Another group of suitable cationic surfactants herein are esters ofquaternary ammonium alcohols, such as quaternary choline esters.

Water-soluble Builder Compound

The detergent compositions of the present invention preferably contain awater-soluble builder compound, typically present at a level of from 1%to 80% by weight, preferably from 10% to 70% by weight, most preferablyfrom 20% to 60% by weight of the composition.

Suitable water-soluble builder compounds include the water solublemonomeric polycarboxylates, or their acid forms, homo or copolymericpolycarboxylic acids or their salts in which the polycarboxylic acidcomprises at least two carboxylic radicals separated from each other bynot more that two carbon atoms, borates, phosphates, and mixtures of anyof the foregoing.

The carboxylate or polycarboxylate builder can be momomeric oroligomeric in type although monomeric polycarboxylates are generallypreferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivativesthereof. Polycarboxylates containing two carboxy groups include thewater-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronicacid and fumaric acid, as well as the ether carboxylates and thesulfinyl carboxylates. Polycarboxylates containing three carboxy groupsinclude, in particular, water-soluble citrates, aconitrates andcitraconates as well as succinate derivatives such as thecarboxymethyloxysuccinates described in British Patent No. 1,379,241,lactoxysuccinates described in British Patent No. 1,389,732, andaminosuccinates described in Netherlands Application 7205873, and theoxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylatesdescribed in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No.3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,439,000.Preferred polycarboxylates are hydroxycarboxylates containing up tothree carboxy groups per molecule, more particularly citrates.

Borate builders, as well as builders containing borate-forming materialsthat can produce borate under detergent storage or wash conditions areuseful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkalimetal tripolyphosphates, sodium, potassium and ammonium pyrophosphate,sodium and potassium and ammonium pyrophosphate, sodium and potassiumorthophosphate, sodium polymeta/phosphate in which the degree ofpolymerization ranges from about 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compound

The detergent compositions of the present invention may contain apartially soluble or insoluble builder compound, typically present at alevel of from 10% to 80% by weight, preferably from 10% to 70% byweight, most preferably from 20% to 60% weight of the composition.

Examples of largely water insoluble builders include the sodiumaluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formulaNaz_(z)[(AlO₂)_(z)(SiO₂)y]. xH₂O. wherein z and y are at least 6; themolar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferablyfrom 7.5 to 276, more preferably from 10 to 264. The aluminosilicatematerial are in hydrated form and are preferably crystalline containingfrom 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, butare preferably synthetically derived. Synthetic crystallinealuminosilicate ion exchange materials are available under thedesignations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS andmixtures thereof. Zeolite A has the formula

Na₁₂[AlO₂)₁₂(SiO₂)₁₂ ].xH₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formulaNa₈₆[(AlO₂)₈₆(SiO₂)₁₀₆].276 H₂O.

Another preferred builder material is a crystalline layered silicate,preferably a crystalline δ-layered silicate, and most preferably thecrystalline δ-layered silicate is a crystalline δ-layered sodiumsilicate with the general formula

NaMSi_(x)O₂₊₁ .yH₂O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is anumber from 0 to 20. Crystalline layered sodium silicates of this typeare disclosed in EP-A-0164514 and methods for their preparation aredisclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the generalformula above preferably has a value of 2, 3 or 4 and is preferably 2.The most preferred material is δ-Na₂Si₂O₅, available from Hoechst AG asNaSKS-6.

The crystalline layered silicate material is preferably present ingranular detergent compositions as a particulate in intimate admixturewith a solid, water-soluble ionisable material. The solid, water-solubleionisable material is selected from organic acids, organic and inorganicacid salts and mixtures thereof.

Organic Peroxyacid Bleaching System

A preferred feature of detergent compositions of the invention is anorganic peroxyacid bleaching system. In one preferred execution thebleaching system contains a hydrogen peroxide source and an organicperoxyacid bleach precursor compound. The production of the organicperoxyacid occurs by an in situ reaction of the precursor with a sourceof hydrogen peroxide. Preferred sources of hydrogen peroxide includeinorganic perhydrate bleaches. In an alternative preferred execution apreformed organic peroxyacid is incorporated directly into thecomposition. Compositions containing mixtures of a hydrogen peroxidesource and organic peroxyacid precursor in combination with a preformedorganic peroxyacid are also envisaged.

Inorganic Perhydrate Bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide.These salts are normally incorporated in the form of the alkali metal,preferably sodium salt at a level of from 1% to 40% by weight, morepreferably from 2% to 30% by weight and most preferably from 5% to 25%by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydratesalts are normally the alkali metal salts. The inorganic perhydrate saltmay be included as the crystalline solid without additional protection.For certain perhydrate salts however, the preferred executions of suchgranular compositions utilize a coated form of the material, such asdescribed in the section ‘delayed release-means ’. Coatings can also beused to provide better storage stability for the perhydrate salt in thegranular product. Suitable coatings therefor comprise inorganic saltssuch as alkali metal silicate, carbonate or borate salts or mixturesthereof, or organic materials such as waxes, oils, or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the formof the monohydrate of nominal formula NaBO₂H₂O₂ or the tetrahydrateNaBO₂H₂O₂.3H₂O.

Alkali metal percarbonates, particularly sodium percarbonate arepreferred perhydrates herein. Sodium percarbonate is an additioncompound having a formula corresponding to 2Na₂CO₃.3H₂O₂, and isavailable commercially as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt ofuse in the detergent compositions herein.

In a preferred aspect of the present invention a means is provided todelay the release to a wash solution of the preferred inorganicperhydrate salts, relatively to the release of the cationic estersurfactant. Said means can comprise equivalents of any of the delayedrelease means herein described for achieving the delayed release of thealkalinity system or species, described hereinbefore.

Peroxyacid Bleach Precursors

Peroxyacid bleach precursors (bleach activators) are preferredperoxyacid sources in accord with the invention. Peroxyacid bleachprecursors are normally incorporated at a level of from 0.5% to 20% byweight, more preferably from 2% to 10% by weight, most preferably from3% to 5% by weight of the compositions.

Suitable peroxyacid bleach precursors typically contain one or more N-or O-acyl groups, which precursors can be selected from a wide range ofclasses. Suitable classes include anhydrides, esters, imides andacylated derivatives of imidazoles and oximes, and examples of usefulmaterials within these classes are disclosed in GB-A-1586789.

Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231and EP-A-0170386. The acylation products of sorbitol, glucose and allsaccharides with benzoylating agents and acetylating agents are alsosuitable.

Specific O-acylated precursor compounds include 2,3,3-tri-methylhexanoyl oxybenzene sulfonates, benzoyl oxybenzene sulfonates,nonanoyl-6-amino caproyl oxybenzene sulfonates, monobenzoyltetraacetylglucose benzoyl peroxide and cationic derivatives of any of the above,including the alkyl ammonium derivatives and pentaacetyl glucose.Phthalic anhydride is a suitable anhydride type precursor.

Specific cationic derivatives of the O-acyl precursor compounds include2-(N,N,N-trimethyl ammonium)ethyl sodium 4-sulphophenyl carbonatechloride, and any of the alkyl ammonium derivatives of the benzoyloxybenzene sulfonates including the 4-(trimethyl ammonium)methylderivative.

Useful N-acyl compounds are disclosed in GB-A-855735, 907356 andGB-A-1246338.

Preferred precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoyl ethylene diamine, N-benzoyl substituted ureasand the N-,N,N¹N¹ tetra acetylated alkylene diamines wherein thealkylene group contains from 1 to 6 carbon atoms, particularly thosecompounds in which the alkylene group contains 1, 2 and 6 carbon atoms.Tetraacetyl ethylene diamine (TAED) is particularly preferred.Preferably, the tetraacetyl ethylene diamine has a compressed particlestructure, achieved by mechanically compression, to delay the desolvingof the particles into the wash solution.

N-acylated precursor compounds of the lactam class are disclosedgenerally in GB-A-955735. Preferred materials comprise the caprolactamsand valerolactams.

Suitable N-acylated lactam precursors have the formula:

wherein n is from 0 to 8, preferably from 0 to 2, and R⁶ is H, an alkyl,aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or asubstituted phenyl group containing from 6 to 18 carbon atoms.

Suitable caprolactam bleach precursors are of the formula:

wherein R¹ is H or an alkyl, aryl, alkoxyaryl or alkaryl groupcontaining from 1 to 12 carbon atoms, preferably from 6 to 12 carbonatoms, most preferably R¹ is phenyl.

Suitable valero lactams have the formula:

wherein R¹ is H or an alkyl, aryl, alkoxyaryl or alkaryl groupcontaining from 1 to 12 carbon atoms, preferably from 6 to 12 carbonatoms. In highly preferred embodiments, R¹ is selected from phenyl,heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixturesthereof.

The most preferred materials are those which are normally solid at <30°C., particularly the phenyl derivatives, ie. benzoyl valerolactam,benzoyl caprolactam and their substituted benzoyl analogues such aschloro, amino alkyl, alkyl, aryl and alkoxy derivatives.

Caprolactam and valerolactam precursor materials wherein the R¹ moietycontains at least 6, preferably from 6 to 12, carbon atoms provideperoxyacids on perhydrolysis of a hydrophobic character which affordnucleophilic and body soil clean-up. Precursor compounds wherein R¹comprises from 1 to 6 carbon atoms provide hydrophilic bleaching specieswhich are particularly efficient for bleaching beverage stains. Mixturesof ‘hydrophobic’ and ‘hydrophilic’ caprolactams and valero lactams,typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be usedherein for mixed stain removal benefits.

Highly preferred caprolactam and valerolactam precursors include benzoylcaprolactam, nonanoyl capro-lactam, benzoyl valerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoyl caprolactam,3,5,5-trimethylhexanoyl valerolactam, octanoyl caprolactam, octanoylvalerolactam, decanoyl caprolactam, decanoyl valerolactarn, undecenoylcaprolactam, undecenoyl valerolactam,(6-octanamidocaproyl)oxybenzene-sulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)-oxybenzenesulfonate, and mixtures thereof.Examples of highly preferred substituted benzoyl lactams includemethylbenzoyl caprolactam, methylbenzoyl valerolactam, ethylbenzoylcaprolactam, ethylbenzoyl valerolactam, propylbenzoyl caprolactam,propylbenzoyl valerolactam, isopropylbenzoyl caprolactam,isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoylvalerolactam, tert-butylbenzoyl caprolactam, tert-butylbenzoylvalerolactam, pentylbenzoyl caprolactam, pentylbenzoyl valerolactam,hexylbenzoyl caprolactam, hexylbenzoyl valerolactam, ethoxybenzoylcaprolactam, ethoxybenzoyl valerolactam, propoxybenzoyl caprolactam,propoxybenzoyl valerolactam, isopropoxybenzoyl caprolactam,isopropoxybenzoyl valerolactam, butoxybenzoyl caprolactam, butoxybenzoylvalerolactam, tert-butoxybenzoyl caprolactam, tert-butoxybenzoylvalerolactam, pentoxybenzoyl caprolactam, pentoxybenzoyl valerolactam,hexoxybenzoyl caprolactam, hexoxybenzoyl valerolactam,2,4,6-trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl valerolactam,pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam,dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam,4-chlorobenzoyl caprolactam, 2,4-dichlororbenzoyl caprolactam,terephthaloyl dicaprolactam, pentafluorobenzoyl caprolactam,pentafluorobenzoyl valerolactam, dichlorobenzoyl valerolactarn,dimethoxybenzoyl valerolactamn, 4-chlorobenzoyl valerolactam,2,4-dichlororbenzoyl valerolactam, terephthaloyl divalerolactam,4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam, and mixturesthereof.

Suitable imidazoles include N-benzoyl imidazole and N-benzoylbenzimidazole and other useful N-acyl group-containing peroxyacidprecursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoylpyroglutamic acid.

Another preferred class of peroxyacid bleach activator compounds are theamide substituted compounds of the following general formulae:

wherein R¹ is an aryl or alkaryl group with from 1 to 14 carbon atoms,R² is an alkylene, arylene, and alkarylene group containing from 1 to 14carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl group containing1 to 10 carbon atoms and L can be essentially any leaving group. R¹preferably contains from 6 to 12 carbon atoms. R² preferably containsfrom 4 to 8 carbon atoms. R¹ may be straight chain or branched alkyl,substituted aryl or alkylaryl containing branching, substitution, orboth and may be sourced from either synthetic sources or natural sourcesincluding for example, tallow fat. Analogous structural variations arepermissible for R². The substitution can include alkyl, aryl, halogen,nitrogen, sulphur and other typical substituent groups or organiccompounds. R⁵ is preferably H or methyl. R¹ and R⁵ should not containmore than 18 carbon atoms in total. Amide substituted bleach activatorcompounds of this type are described in EP-A-0170386.

The L group must be sufficiently reactive for the reaction to occurwithin the optimum time frame (e.g., a wash cycle). However, if L is tooreactive, this activator will be difficult to stabilize for use in ableaching composition. These characteristics are generally paralleled bythe pKa of the conjugate acid of the leaving group, although exceptionsto this convention are known. Ordinarily, leaving groups that exhibitsuch behavior are those in which their conjugate acid has a pKa in therange of from 4 to 13, preferably from 6 to 11 and most preferably from8 to 11.

Preferred bleach precursors are those wherein R¹, R² and R⁵ are asdefined for the amide substituted compounds and L is selected from thegroup consisting of:

and mixture thereof, wherein R¹ is an alkyl, aryl, or alkaryl groupcontaining from 1 to 14 carbon atoms, R³ is an alkyl chain containingfrom 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizinggroup.

The preferred solubilizing groups are —SO₃ ⁻M⁺, —CO₂ ⁻M⁺, —SO₄ ⁻M⁺,—N⁺(R³)₄X⁻ and O←N(R³)₃ and most preferably —SO₃ ⁻M⁺ and —CO₂ ⁻M⁺wherein R³ is an alkyl chain containing from 1 to 4 carbon atoms, M is acation which provides solubility to the bleach activator and X is ananion which provides solubility to the bleach activator. Preferably, Mis an alkali metal, ammonium or substituted ammonium cation, with sodiumand potassium being most preferred, and X is a halide, hydroxide,methylsulfate or acetate anion. It should be noted that bleachactivators with a leaving group that does not contain a solubilizinggroups should be well dispersed in the bleaching solution in order toassist in their dissolution.

Preferred examples of bleach activators of the above formulae include(6-octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.

Other preferred precursor compounds include those of thebenzoxazin-type, having the formula:

including the substituted benzoxazins of the type

wherein R₁ is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R₂, R₃,R₄, and R₅ may be the same or different substituents selected from H,halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino,COOR₆ (wherein R₆ is H or an alkyl group) and carbonyl functions.

An especially preferred precursor of the benzoxazin-type is:

Bleach Catalyst

The detergent compositions optionally contain a transition metalcontaining bleach catalyst. One suitable type of bleach catalyst is acatalyst system comprising a heavy metal cation of defined bleachcatalytic activity, such as copper, iron or manganese cations, anauxiliary metal cation having little or no bleach catalytic activity,such as zinc or aluminum cations, and a sequestrant having definedstability constants for the catalytic and auxiliary metal cations,particularly ethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water-soluble saltsthereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexesdisclosed in U.S. Pat. No. 5,246,621 and 5,244,594. Preferred examplesof these catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(PF₆)₂, Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄-(ClO₄)₂, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₃, andmixtures thereof. Others are described in European patent applicationpublication no. 549,272. Other ligands suitable for use herein include1,5,9-trimethyl-1,5,9-triazacyclododecane,2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane,1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

For examples of suitable bleach catalysts see U.S. Pat. Nos. 4,246,612and 5,227,084. See also U.S. Pat. No. 5,194,416 which teachesmononuclear manganese (IV) complexes such asMn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH₃)₃—(PF₆). Still anothertype of bleach catalyst, as disclosed in U.S. Pat. No. 5,114,606, is awater-soluble complex of manganese (III), and/or (IV) with a ligandwhich is a non-carboxylate polyhydroxy compound having at least threeconsecutive C—OH groups. Other examples include binuclear Mn complexedwith tetra-N-dentate and bi-N-dentate ligands, includingN₄Mn^(III)(u-O)₂Mn^(IV)N₄)⁺ and[Bipy₂Mn^(III)(u-O)₂Mn^(IV)bipy₂]-(ClO₄)₃.

Further suitable bleach catalysts are described, for example, inEuropean patent application No. 408,131 (cobalt complex catalysts),European patent applications, publication nos. 384,503, and 306,089(metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455(manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 andEuropean patent application, publication no. 224,952, (absorbedmanganese on aluminosilicate catalyst), U.S. Pat. No. 4,601,845(aluminosilicate support with manganese and zinc or magnesium salt),U.S. Pat. No. 4,626,373 (manganese/ligand catalyst), U.S. Pat. No.4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019(cobalt chelant catalyst) Canadian 866,191 (transition metal-containingsalts), U.S. Pat. No. 4,430,243 (chelants with manganese cations andnon-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganesegluconate catalysts).

Heavy Metal Ion Sequestrant

The detergent compositions of the invention preferably contain as anoptional component a heavy metal ion sequestrant. By heavy metal ionsequestrant it is meant herein components which act to sequester(chelate) heavy metal ions. These components may also have calcium andmagnesium chelation capacity, but preferentially they show selectivityto binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25%to 7.5% and most preferably from 0.5% to 5% by weight of thecompositions.

Suitable heavy metal ion sequestrants for use herein include organicphosphonates, such as the amino alkylene poly (alkylene phosphonates),alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylenephosphonates.

Preferred among the above species are diethylene triaminepenta(methylene phosphonate), ethylene diamine tri(methylenephosphonate)hexamethylene diamine tetra(methylene phosphonate) andhydroxy-ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein includenitrilotriacetic acid and polyaminocarboxylic acids such asethylenediaminotetracetic acid, ethylenetriamine pentacetic acid,ethylenediamine disuccinic acid, ethylenediamine diglutaric acid,2-hydroxypropylenediamine disuccinic acid or any salts thereof.Especially preferred is ethylenediamine-N,N′-disuccinic acid (EDDS) orthe alkali metal, alkaline earth metal, ammonium, or substitutedammonium salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein areiminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid orglyceryl imino diacetic acid, described in EP-A-317,542 andEP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid andaspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acidsequestrants described in EP-A-516,102 are also suitable herein. Theβ-alanine-N,N′-diacetic acid, aspartic acid-N,N′-diacetic acid, asparticacid-N-monoacetic acid and iminodisuccinic acid sequestrants describedin EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331describes suitable sequestrants derived from collagen, keratin orcasein. EP-A-528,859 describes a suitable alkyl iminodiacetic acidsequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylicacid are alos suitable. Glycinamide-N,N′-disuccinic acid (GADS),ethylenediamine-N-N′-diglutaric acid (EDDG) and2-hydroxypropylenediamine-N-N′-disuccinic acid (HPDDS) are alsosuitable.

Enzyme

Another preferred ingredient useful in the detergent compositions is oneor more additional enzymes.

Preferred additional enzymatic materials include the commerciallyavailable lipases, cutinases, amylases, neutral and alkaline proteases,esterases, cellulases, pectinases, lactases and peroxidasesconventionally incorporated into detergent compositions. Suitableenzymes are discussed in U.S. Pat. Nos. 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those soldunder the tradenames Alcalase, Savinase, Primase, Durazym, and Esperaseby Novo Industries A/S (Denmark), those sold under the tradenameMaxatase, Maxacal and Maxapem by Gist-Brocades, those sold by GenencorInternational, and those sold under the tradename Opticlean and Optimaseby Solvay Enzymes. Protease enzyme may be incorporated into thecompositions in accordance with the invention at a level of from 0.0001%to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from aspecial strain of B licheniformis, described in more detail inGB-1,269,839 (Novo). Preferred commercially available amylases includefor example, those sold under the tradename Rapidase by Gist-Brocades,and those sold under the tradename Termamyl and BAN by Novo IndustriesA/S. Amylase enzyme may be incorporated into the composition inaccordance with the invention at a level of from 0.0001% to 2% activeenzyme by weight of the composition.

Preferably the detergent composition in accordance with the presentinvention contains a lipolytic enzyme. It has been found that thecationic ester surfactant enhances the performance of the lipolyticenzyme. Two mechanisms are believed to be responsible for the improvedenzyme performance. Firstly, the fatty acids, which are formed by theenzymatic reaction of the lipolytic enzymes with triglycerides containedin the greasy or oily soils, will be removed from the fabric surface bythe cationic ester surfactant. This will facilitate the ‘access’ by theenzymes to the greasy stains/soils during the washing process. Secondly,the removal of fatty acids from the fabric surface by the cationic estersurfactant will reduce the formation and deposition onto the fabric of‘lime soap’, formed through reaction of fatty acids with calcium ions ofthe hardness of the water. This will also facilitate the ‘access’ by theenzymes to the greasy stains/soils on the fabric surface.

Lipolytic enzyme may be present at levels of active lipolytic enzyme offrom 0.01% to 5% by weight, preferably 0.1% to 2% by weight, mostpreferably from 0.1% to 0.5% by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, forexample, from a lipase producing strain of Humicola sp., Thermomyces sp.or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomasfluorescens. Lipase from chemically or genetically modified mutants ofthese strains are also useful herein. A preferred lipase is derived fromPseudomonas pseudoalcaligenes, which is described in Granted EuropeanPatent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene fromHumicola lanuginosa and expressing the gene in Aspergillus oryza, ashost, as described in European Patent Application, EP-A-0258 068, whichis commercially available from Novo Industri A/S, Bagsvaerd, Denmark,under the trade name Lipolase. This lipase is also described in U.S.Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989. A highlypreferred lipase, which is also obtained via Humicola lanuginosa, is alipase known as Lipase Ultra SP514 (trade name), also available fromNOVO Industri A/S.

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components of thedetergent compositions in accord with the invention, and are preferablypresent as components of any particulate components where they may actsuch as to bind the particulate component together. By organic polymericcompound it is meant herein essentially any polymeric organic compoundcommonly used as dispersants, and anti-redeposition and soil suspensionagents in detergent compositions, including any of the high molecularweight organic polymeric compounds described as clay flocculating agentsherein.

Organic polymeric compound is typically incorporated in the detergentcompositions of the invention at a level of from 0.1% to 30%, preferablyfrom 0.5% to 15%, most preferably from 1% to 10% by weight of thecompositions.

Examples of organic polymeric compounds include the water solubleorganic homo- or co-polymeric polycarboxylic acids or their salts inwhich the polycarboxylic acid comprises at least two carboxyl radicalsseparated from each other by not more than two carbon atoms. Polymers ofthe latter type are disclosed in GB-A-1,596,756. Examples of such saltsare polyacrylates of MWt 2000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 20,000 to100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived fromaspartic acid such as those disclosed in EP-A-305282, EP-A-305283 andEP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylicacid, polyaspartic acid and vinyl alcohol, particularly those having anaverage molecular weight of from 5,000 to 10,000, are also suitableherein.

Other organic polymeric compounds suitable for incorporation in thedetergent compositions herein include cellulose derivatives such asmethylcellulose, carboxymethylcellulose, hydroxypropylmethylcelluloseand hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000.

Other organic polymeric compounds suitable for incorporation in thedetergent compositions herein include cellulose derivatives such asmethylcellulose, carboxymethylcellulose, hydroxypropylmethylcelluloseand hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000.

Another organic compound, which is a preferred claydispersant/anti-redeposition agent, for use herein, can be theethoxylated cationic monoamines and diamines of the formula:

wherein X is a nonionic group selected from the group consisting of H,C₁-C₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof,a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene,hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least16, with a typical range of from 20 to 35; for cationic diamines (b=1),n is at least about 12 with a typical range of from about 12 to about42.

Other dispersants/anti-redeposition agents for use herein are describedin EP-B-011965 and U.S. Pat. Nos. 4,659,802 and 4,664,848.

Suds Supressing System

The detergent compositions of the invention, when formulated for use inmachine washing compositions, preferably comprise a suds suppressingsystem present at a level of from 0.01% to 15%, preferably from 0.05% to10%, most preferably from 0.1% to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for example siliconeantifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures ofcompounds which act such as to depress the foaming or sudsing producedby a solution of a detergent composition, particularly in the presenceof agitation of that solution.

Particularly preferred antifoam compounds for use herein are siliconeantifoam compounds defined herein as any antifoam compound including asilicone component. Such silicone antifoam compounds also typicallycontain a silica component. The term “silicone” as used herein, and ingeneral throughout the industry, encompasses a variety of relativelyhigh molecular weight polymers containing siloxane units and hydrocarbylgroup of various types. Preferred silicone antifoam compounds are thesiloxanes, particularly the polydimethylsiloxanes having trimethylsilylend blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acidsand soluble salts thereof. These materials are described in U.S. Pat.No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Themonocarboxylic fatty acids, and salts thereof, for use as sudssuppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,preferably 12 to 18 carbon atoms. Suitable salts include the alkalimetal salts such as sodium, potassium, and lithium salts, and ammoniumand alkanolammonium salts. A disadvantage associated with such fattyacid antifoams is their tendency to interact with any Ca⁺⁺ or Mg⁺⁺ ionpresent in the wash solution, to form insoluble ‘lime soaps’, which candeposit on the fabric in the wash. It has now been found that thisproblem can be reduced by the presence of cationic ester surfactants.The cationic ester surfactant interacts with the formed ‘lime soaps’,thereby suspending them in the wash solution, and thus reducing thedeposition of the formed ‘lime soaps’ on the fabric in the wash.

Other suitable antifoam compounds include, for example, high molecularweight fatty esters (e.g. fatty acid triglycerides), fatty acid estersof monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g. stearone)N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amideand monostearyl di-alkali metal (e.g. sodium, potassium, lithium)phosphates and phosphate esters.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, mostpreferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75%to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% byweight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at alevel of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycolrake copolymer with a polyoxyalkylene content of 72-78% and an ethyleneoxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level offrom 0.5% to 10%, preferably 1% to 10% by weight; a particularlypreferred silicone glycol rake copolymer of this type is DCO544,commercially available from DOW Corning under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising aC₁₆-C₁₈ ethoxylated alcohol with a degree of ethoxylation of from 5 to50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to70%, by weight;

A highly preferred particulate suds suppressing system is described inEP-A-0210731 and comprises a silicone antifoam compound and an organiccarrier material having a melting point in the range 50° C. to 85° C.,wherein the organic carrier material comprises a monoester of glyceroland a fatty acid having a carbon chain containing from 12 to 20 carbonatoms. EP-A-0210721 discloses other preferred particulate sudssuppressing systems wherein the organic carrier material is a fatty acidor alcohol having a carbon chain containing from 12 to 20 carbon atoms,or a mixture thereof, with a melting point of from 45° C. to 80° C.

Clay Softening System

The detergent compositions may contain a clay softening systemcomprising a clay mineral compound and optionally a clay flocculatingagent.

The clay mineral compound is preferably a smectite clay compound.Smectite clays are disclosed in the U.S. Pat. Nos. 3,862,058, 3,948,790,3,954,632 and 4,062,647. European Patents Nos. EP-A-299,575 andEP-A-313,146 in the name of the Procter and Gamble Company describesuitable organic polymeric clay flocculating agents.

Polymeric Dye Transfer Inhibiting Agents

The detergent compositions herein may also comprise from 0.01% to 10%,preferably from 0.05% to 0.5% by weight of polymeric dye transferinhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polyamine N-oxide Polymers

Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure formula:

wherein P is a polymerisable unit, and

R are aliphatic, ethoxylated aliphatics, aromatic heterocyclic oralicyclic groups or any combination thereof whereto the nitrogen of theN—O group can be attached or wherein the nitrogen of the N—O group ispart of these groups.

The N—O group can be represented by the following general structures:

wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic oralicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1and wherein the nitrogen of the N—O group can be attached or wherein thenitrogen of the N—O group forms part of these groups. The N—O group canbe part of the polymerisable unit (P) or can be attached to thepolymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N—O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selectedfrom aliphatic, aromatic, alicyclic or heterocyclic groups. One class ofsaid polyamine N-oxides comprises the group of polyamine N-oxideswherein the nitrogen of the N—O group forms part of the R-group.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine,quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto theN—O group is attached to the polymerisable unit. A preferred class ofthese polyamine N-oxides comprises the polyamine N-oxides having thegeneral formula (I) wherein R is an aromatic, heterocyclic or alicyclicgroups wherein the nitrogen of the N—O functional group is part of saidR group. Examples of these classes are polyamine oxides wherein R is aheterocyclic compound such as pyrridine, pyrrole, imidazole andderivatives thereof.

The polyamine N-oxides can be obtained in almost any degree ofpolymerisation. The degree of polymerisation is not critical providedthe material has the desired water-solubility and dye-suspending power.Typically, the average molecular weight is within the range of 500 to1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are coploymers of N-vinylimidazole andN-vinylpyrrolidone having an average molecular weight range of from5,000 to 50,000. The preferred copolymers have a molar ratio ofN-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone(“PVP”) having an average molecular weight of from 2,500 to 400,000.Suitable polyvinylpyrrolidones are commercially vailable from ISPCorporation, New York, N.Y. and Montreal, Canada under the product namesPVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (averagemolecular weight of 40,000), PVP K-60 (average molecular weight of160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15is also available from ISP Corporation. Other suitablepolyvinylpyrrolidones which are commercially available from BASFCooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidonesas polymeric dye transfer inhibiting agents. Said polyvinyloxazolidoneshave an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole aspolymeric dye transfer inhibiting agent. Said polyvinylimidazolespreferably have an average molecular weight of from 2,500 to 400,000.

Optical Brightener

The detergent compositions herein also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners.

Hydrophilic optical brighteners useful herein include those having thestructural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Cationic Fabric Softening Agents

Cationic fabric softening agents can also be incorporated intocompositions in accordance with the present invention. Suitable cationicfabric softening agents include the water insoluble tertiary amines ordilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0011 340.

Cationic fabric softening agents are typically incorporated at totallevels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the compositions ofthe invention include perfumes, colours and filler salts, with sodiumsulfate being a preferred filler salt.

pH of the Compositions

The present compositions preferably have a pH measured as a 1% solutionin distilled water of at least 9.0, preferably from 9.0 to 11.5, mostpreferably from 9.5 to 10.5.

Form of the Compositions

The detergent composition of the invention can be made via a variety ofmethods, including spray-drying, dry-mixing and agglomerating of thevarious compounds comprised in the detergent composition. The acidicsource of the invention is preferably dry-added.

The compositions in accordance with the invention can take a variety ofphysical forms including granular, tablet, bar and liquid forms. Thecompositions are particularly the so-called concentrated granulardetergent compositions adapted to be added to a washing machine by meansof a dispensing device placed in the machine drum with the soiled fabricload. The detergent is preferably a blown powder, whereby the sulphatecomponents is comprised in the blown powder or is dry-added.

The mean particle size of the components of granular compositions inaccordance with the invention can be from 0.1 mm to 5.0 mm, but itshould preferably be such that no more that 5% of particles are greaterthan 1.7 mm in diameter and not more than 5% of particles are less than0.15 mm in diameter.

The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of Tyler sieves. The weight fractions therebyobtained are plotted against the aperture size of the sieves.

The mean particle size is taken to be the aperture size through which50% by weight of the sample would pass.

The granular detergent compositions in accordance with the presentinvention typically have a bulk density of at least 500 g/liter,preferably less than 850 g/liter more preferably from 600 g/liter to 750g/liter. Bulk density is measured by means of a simple funnel and cupdevice consisting of a conical funnel moulded rigidly on a base andprovided with a flap valve at its lower extremity to allow the contentsof the funnel to be emptied into an axially aligned cylindrical cupdisposed below the funnel. The funnel is 130 mm high and has internaldiameters of 130 mm and 40 mm at its respective upper and lowerextremities. It is mounted so that the lower extremity is 140 mm abovethe upper surface of the base. The cup has an overall height of 90 mm,an internal height of 87 mm and an internal diameter of 84 mm. Itsnominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by handpouring, the flap valve is opened and powder allowed to overfill thecup. The filled cup is removed from the frame and excess powder removedfrom the cup by passing a straight edged implement eg; a knife, acrossits upper edge. The filled cup is then weighed and the value obtainedfor the weight of powder doubled to provide a bulk density in g/liter.Replicate measurements are made as required.

Surfactant Agglomerate Particles

The surfactant system herein is can be present in granular compositionsin the form of surfactant agglomerate particles, which may take the formof flakes, prills, marumes, noodles, ribbons, but preferably take theform of granules. The most preferred way to process the particles is byagglomerating powders (e.g. aluminosilicate, carbonate) with high activesurfactant pastes and to control the particle size of the resultantagglomerates within specified limits. Such a process involves mixing aneffective amount of powder with a high active surfactant paste in one ormore agglomerators such as a pan agglomerator, a Z-blade mixer or morepreferably an in-line mixer such as those manufactured by Schugi(Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, andGebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used,such as a Lodige CB (Trade Name).

Alternatively, the surfactants or part thereof is comprised in the blownpowder, as mentioned above.

Laundry Washing Method

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 40 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65liters, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash cycle. Its volume capacityshould be such as to be able to contain sufficient detergent product aswould normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensingdevice containing the detergent product is placed inside the drum. Atthe commencement of the wash cycle of the washing machine water isintroduced into the drum and the drum periodically rotates. The designof the dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product duringthe wash cycle in response to its agitation as the drum rotates and alsoas a result of its contact with the wash water.

To allow for release of the detergent product during the wash the devicemay possess a number of openings through which the product may pass.Alternatively, the device may be made of a material which is permeableto liquid but impermeable to the solid product, which will allow releaseof dissolved product. Preferably, the detergent product will be rapidlyreleased at the start of the wash cycle thereby providing transientlocalised high concentrations of product in the drum of the washingmachine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a waythat container integrity is maintained in both the dry state and duringthe wash cycle. Especially preferred dispensing devices for use with thecomposition of the invention have been described in the followingpatents; GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 andEP-A-0288346. An article by J. Bland published in Manufacturing Chemist,November 1989, pages 41-46 also describes especially preferreddispensing devices for use with granular laundry products which are of atype commonly know as the “granulette”. Another preferred dispensingdevice for use with the compositions of this invention is disclosed inPCT Patent Application No. WO94/11562.

Especially preferred dispensing devices are disclosed in European PatentApplication Publication Nos. 0343069 & 0343070. The latter Applicationdiscloses a device comprising a flexible sheath in the form of a bagextending from a support ring defining an orifice, the orifice beingadapted to admit to the bag sufficient product for one washing cycle ina washing process. A portion of the washing medium flows through theorifice into the bag, dissolves the product, and the solution thenpasses outwardly through the orifice into the washing medium. Thesupport ring is provided with a masking arrangement to prevent egress ofwetted, undissolved, product, this arrangement typically comprisingradially extending walls extending from a central boss in a spoked wheelconfiguration, or a similar structure in which the walls have a helicalform. These patent applications explicitely discribe the use of suchdevices for high density and other detergents in general, however whenlow density detergents, in accord with the present invention, are usedthe size of the dispensing device should be adjusted to the volume ofthe low density detergent which is preferably used for one wash cycle.

Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated with awater impermeable protective material so as to retain the contents, suchas is disclosed in European published Patent Application No. 0018678.Alternatively it may be formed of a water-insoluble synthetic polymericmaterial provided with an edge seal or closure designed to rupture inaqueous media as disclosed in European published Patent Application Nos.0011500, 0011501, 0011502, and 0011968. A convenient form of waterfrangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric filmsuch as polyethylene or polypropylene.

Packaging for the Compositions

Commercially marketed executions of the bleaching compositions can bepackaged in any suitable container including those constructed frompaper, cardboard, plastic materials and any suitable laminates. Apreferred packaging execution is described in European Application No.94921505.7.

Abbreviations Used in Following Examples

In the detergent compositions, the abbreviated component identificationshave the following meanings:

LAS Sodium linear C₁₂ alkyl benzene sulfonate TAS Sodium tallow alkylsulfate C45AS Sodium C₁₄-C₁₅ linear alkyl sulfate CxyEzS SodiumC_(1x)-C_(1y) branched alkyl sulfate condensed with z moles of ethyleneoxide C45E7 A C₁₄ ₋₁₅ predominantly linear primary alcohol condensedwith an average of 7 moles of ethylene oxide C25E3 A C₁₂₋₁₅ branchedprimary alcohol condensed with an average of 3 moles of ethylene oxideC25E5 A C₁₂₋₁₅ branched primary alcohol condensed with an average of 5moles of ethylene oxide CEQ R₁COOCH₂CH₂.N⁺(CH₃)₃ with R₁ = C₁₁-C₁₃ QASR₂.N⁺(CH₃)₂(C₂H₄OH) with R₂ = C₁₂-C₁₄ Soap Sodium linear alkylcarboxylate derived from an 80/20 mixture of tallow and coconut oils.TFAA C₁₆-C₁₈ alkyl N-methyl glucamide TPKFA C₁₂-C₁₄ topped whole cutfatty acids STPP Anhydrous sodium tripolyphosphate Zeolite A HydratedSodium Aluminosilicate of formula Na₁₂(A10₂SiO₂)₁₂.27H₂O having aprimary particle size in the range from 0.1 to 10 micrometers NaSKS-6Crystalline layered silicate of formula δ-Na₂Si₂O₅ Citric acid Anhydrouscitric acid Carbonate Anhydrous sodium carbonate with a particle sizebetween 200 μm and 900 μm Bicarbonate Anhydrous sodium bicarbonate witha particle size distribution between 400 μm and 1200 μm SilicateAmorphous Sodium Silicate (SiO₂:Na₂O; 2.0 ratio) Sodium sulfateAnhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate ofactivity 86.4% with a particle size distribution between 425 μm and 850μm MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecular weightabout 70,000. CMC Sodium carboxymethyl cellulose Protease Proteolyticenzyme of activity 4 KNPU/g sold by NOVO Industries A/S under thetradename Savinase Alcalase Proteolytic enzyme of activity 3 AU/g soldby NOVO Industries A/S Cellulase Cellulytic enzyme of activity 1000CEVU/g sold by NOVO Industries A/S under the tradename Carezyme AmylaseAmylolytic enzyme of activity 60 KNU/g sold by NOVO Industries A/S underthe tradename Termamyl 60T Lipase Lipolytic enzyme of activity 100 KLU/gsold by NOVO Industries A/S under the tradename Lipolase EndolaseEndoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/SPB4 Sodium perborate tetrahydrate of nominal formula NaBO₂.3H₂O.H₂O₂ PB1Anhydrous sodium perborate monohydrate bleach of nominal formulaNaBO₂.H₂O₂ Percarbonate Sodium Percarbonate of nominal formula2Na₂CO₃.3H₂O₂ NOBS Nonanoyloxybenzene sulfonate in the form of thesodium salt. TAED Tetraacetylethylenediamine DTPMP Diethylene triaminepenta (methylene phosphonate), marketed by Monsanto under the Trade nameDequest 2060 Photoactivated Sulfonated Zinc Phthlocyanine encapsulatedin bleach dextrin soluble polymer Brightener 1 Disodium4,4′-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium4,4′-bis(4-anilino-6-morpholino-1.3.5- triazin-2-yl)amino)stilbene-2:2′-disulfonate. HEDP 1,1-hydroxyethane diphosphonic acid PVNOPolyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone andvinylimidazole SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxyand terephtaloyl backbone SRP 2 Diethoxylated poly (1, 2 propyleneterephtalate) short block polymer Silicone antifoam Polydimethylsiloxanefoam controller with siloxane-oxyalkylene copolymer as dispersing agentwith a ratio of said foam controller to said dispersing agent of 10:1 to100:1. Alkalinity % weight equivalent of NaOH, as obtained using thealkalinity release test method described herein.

In the following Examples all levels are quoted as % by weight of thecomposition:

EXAMPLE 1

The following granular laundry detergent compositions A, B, C and D ofbulk density 650 g/liter were prepared in accord with the invention:

A B C D LAS 5.61 4.76 6.0 7.0 TAS 1.86 1.57 1.4 1.3 C45AS 2.24 3.89 2.22.2 C25AE3S 0.76 1.18 1.18 1.18 C45E7 — 5.0 — 5.0 C25E3 5.5 — 5.0 — QAS2.0 2.0 — — STPP — — — — Zeolite A 19.5 19.5 15.5 15.5 NaSKS-6/citricacid (79:21) 10.6 10.6 10.6 8.6 Carbonate 21.4 21.4 15.4 17.1Bicarbonate 2.0 2.0 — — Silicate — — — — Sodium sulfate 15.0 17.0 16.518.5 PB4 12.7 — — 10.3 TAED 3.1 — — 2.1 DETPMP 0.2 0.2 0.2 0.2 HEDP 0.30.3 0.3 0.3 Protease 0.85 0.85 0.05 0.85 Lipase 0.15 0.15 0.15 0.15Cellulase 0.28 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 0.1 MA/AA 1.6 1.6 1.61.6 CMC 0.4 0.4 0.4 0.4 Photoactivated bleach (ppm) 27 ppm 27 ppm 27 ppm27 ppm Brightener 1 0.19 0.19 0.19 0.19 Brightener 2 0.04 0.04 0.04 0.04Perfume 0.3 0.3 0.3 0.3 Silicone antifoam 2.4 2.4 2.4 2.4 Citric acid4.5 2.0 3.0 6.0 Minors/misc to 100%

EXAMPLE 2

The following detergent formulations, according to the present inventionwere prepared.

E F G Blown Powder STPP 14.0 — 14.0 Zeolite A — 20.0 — C45AS 9.0 6.0 8.0MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 9.0 TAS 2.0 — — CEQ — 3.0 3.5 Silicate 7.08.0 8.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Siliconeantifoam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 26.023.0 25.0 PB4 18.0 18.0 10 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivatedbleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase0.25 0.30 0.15 Dry mixed sodium sulfate 15.0 18.0 22.0 Citric acid 2.52.0 5.0 Balance (Moisture & 100.0 100.0 100.0 Miscellaneous) Density(g/liter) 630 670 670

EXAMPLE 3

The following nil bleach-containing detergent formulations of particularuse in the washing of colored clothing, according to the presentinvention were prepared:

H I Blown Powder Zeolite A 15.0 — Sodium sulfate 5.0 — LAS 3.0 — CEQ 0.41.3 DTPMP 0.4 — CMC 0.4 — MA/AA 4.0 — Agglomerates C45A5 — 11.0 LAS 6.0— TAS 3.0 — Silicate 4.0 — Zeolite A 10.0 13.0 CMC — 0.5 MA/AA — 2.0Carbonate 9.0 7.0 Spray On Perfume 0.3 0.5 C45E7 4.0 4.0 C25E3 2.0 2.0Dry additives MA/AA — 3.0 NaSKS-6 — 12.0 Citric acid 4.0 3.0 Citrate10.0 8.0 Bicarbonate 7.0 5.0 Carbonate 8.0 7.0 PVPVI/PVNO 0.5 0.5Alcalase 0.5 0.9 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate 10.5 19.5 Balance(Moisture and Miscellaneous) 100.0 100.0 Density (g/liter) 700 700

EXAMPLE 4

The following detergent formulations, according to the present inventionwere prepared:

J K L M LAS 12.0 12.0 12.0 10.0 QAS 0.7 1.0 — 0.7 TFAA — 1.0 — —C25E5/C45E7 — 2.0 — 0.5 C45E3S — 3.0 — — CEQ 2.0 — 1.0 — STPP 30.0 18.015.0 — Silicate 9.0 7.0 10.0 — Carbonate 15.0 10.5 15.0 25.0 Bicarbonate— 4.0 — — Sodium Sulphate 18.0 16.5 21.5 20.5 DTPMP 0.7 1.0 — — SRP 10.3 0.2 — 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.00.5 0.5 Amylase 0.8 0.4 — 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.150.05 — — Photoactivated 70 ppm 45 ppm — 10 ppm bleach (ppm) Brightener 10.2 0.2 0.08 0.2 PB1 6.0 2.0 — — NOBS 2.0 1.0 — — Citric acid 3.5 5.02.5 6.0 Balance (Moisture 100 100 100 100 and Miscellaneous)

EXAMPLE 5

The following detergent formulations, according to the present inventionwere prepared:

N O P Blown Powder Zeolite A 10.0 15.0 6.0 Sodium sulfate 19.0 15.0 7.0MA/AA 3.0 3.0 6.0 LAS 10.0 8.0 10.0 C45AS 4.0 5.0 7.0 CEQ 2.0 — 2.0Silicate — 1.0 7.0 Soap — — 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 28.018.0 20.0 DTPMP — 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 Dry additivesPVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS — 6.1 4.5 PBI 1.0 5.0 6.0 Sodiumsulfate — 6.0 — Citric acid 4.5 1.4 5.0 Balance (Moisture and 100 100100 Miscellaneous)

EXAMPLE 6

The following bleach-containing detergent formulations, according to thepresent invention were prepared:

Q R Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 12.0 LAS 3.0 3.0QAS — 1.5 CEQ 2.0 — DTPMP 0.4 0.4 CMC 0.4 0.4 MA/AA 4.0 2.0 AgglomeratesLAS 4.0 4.0 TAS 2.0 1.0 Silicate 3.0 4.0 Zeolite A 8.0 8.0 Carbonate 8.06.0 Spray On Perfume 0.3 0.3 C45E7 2.0 2.0 C25E3 2.0 — Dry additivesCitric acid 5.0 3.0 Citrate 5.0 2.0 Bicarbonate — — Carbonate 8.0 10.0TAED 6.0 5.0 PB1 14.0 10.0 Polyethylene oxide of MW 5,000,000 — 0.2Bentonite clay — 10.0 Protease 1.0 1.0 Lipase 0.4 0.4 Amylase 0.6 0.6Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate18.0 4.0 Balance (Moisture and 100.0 100.0 Miscellaneous)

EXAMPLE 7

The following detergent formulations, according to the present inventionwere prepared:

S T Agglomerate C45AS 11.0 14.0 CEQ 3.0 3.5 Zeolite A 15.0 6.0 Carbonate4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 Spray On C25E5 5.0 5.0Perfume 0.5 0.5 Dry Adds Citric acid 1.5 2.0 HBDP 0.5 0.3 SKS 6 13.010.0 Citrate 3.0 1.0 TAED 5.0 7.0 Sodium Sulphate 16.0 19.5 Percarbonate20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.60.6 Amylase 0.6 0.6 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2Brightener 2 0.2 — Balance (Moisture and 100 100 Miscellaneous)

What is claimed is:
 1. A granular detergent composition comprising atleast 15% by weight of a sulphate salt, from about 1% to about 7% of anacid dispersing aid wherein at least 80% by weight of the aciddispersing aid has a particle size of from 150 μm to about 710 μm, andan alkali source having a particle size of from about 250 μm or greater,wherein said acid dispersing aid and alkali source are capable ofreacting together in the presence of water to produce a gas, wherein theweight ratio of sulphate salt to said acid dispersing aid is from 13.5:1or less, and wherein the acid dispersing aid is added as a separategranular component.
 2. A detergent composition according to claim 1wherein the alkali source comprises an alkaline salt selected from analkali metal or alkaline earth metal carbonate, bicarbonate,sesqui-carbonate, or alkali metal percarbonate salt.
 3. A detergentcomposition according to claim 1 wherein the acid dispersing aidcomprises an organic, mineral or inorganic acid.
 4. A detergentcomposition according to claim 3 wherein the acid dispersing aid iscitric acid, glutaric acid, tartaric acid, succinic acid, adipic acid,monosodium phosphate, or boric acid or mixtures thereof.
 5. A detergentcomposition according to claim 4 wherein the acid dispersing aid iscitric acid.
 6. A detergent composition according to claim 1 wherein thealkali source is present in an amount of from 5% to 60% by weight of thecomposition.
 7. A detergent composition according to claim 1 wherein thesulphate salt is present at a level of at least 20.5% by weight, theacid dispersing aid is present from about 1% to about 10% by weight andthe ratio of sulphate salt to acid dispersing aid is from 13.5:1 orless.
 8. A detergent composition according to claim 1 wherein saidsulphate is sodium sulphate or is a mixture of sodium sulphate and offrom 0.2% to 5% by weight of magnesium sulphate.
 9. A detergentcomposition according to claim 1, wherein the ratio of sulphate salt toacid dispersing aid is from 11:1 to 2:1.
 10. A detergent compositionaccording to claim 1, having a bulk density of less than 850 gr/liter.11. A detergent composition according to claim 1 wherein the aciddispersing aid is capable of building or dispersing free ions present inthe wash.
 12. A method of washing laundry in a domestic washing machinecomprising, introducing into a dispensing device which is placed in thedrum of the washing machine, or introducing into the dispensing drawerof a washing machine, an effective amount of a detergent compositionaccording to claim 1.